EP2203945A1 - Optoelektronische vorrichtung - Google Patents
Optoelektronische vorrichtungInfo
- Publication number
- EP2203945A1 EP2203945A1 EP08841820A EP08841820A EP2203945A1 EP 2203945 A1 EP2203945 A1 EP 2203945A1 EP 08841820 A EP08841820 A EP 08841820A EP 08841820 A EP08841820 A EP 08841820A EP 2203945 A1 EP2203945 A1 EP 2203945A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- optoelectronic device
- fluorine
- polymer
- function
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000005693 optoelectronics Effects 0.000 title claims abstract description 51
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 69
- 239000011737 fluorine Substances 0.000 claims abstract description 66
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 230000003993 interaction Effects 0.000 claims abstract description 18
- WCQRWCFGZARAMR-UHFFFAOYSA-N [F].[F] Chemical compound [F].[F] WCQRWCFGZARAMR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000007772 electrode material Substances 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 122
- 238000002347 injection Methods 0.000 claims description 33
- 239000007924 injection Substances 0.000 claims description 33
- 229920001940 conductive polymer Polymers 0.000 claims description 30
- 229920000767 polyaniline Polymers 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000004020 conductor Substances 0.000 claims description 15
- 229920002313 fluoropolymer Polymers 0.000 claims description 13
- 238000004770 highest occupied molecular orbital Methods 0.000 claims description 12
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 10
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 10
- 150000003384 small molecules Chemical class 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000009832 plasma treatment Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 7
- 230000000903 blocking effect Effects 0.000 claims description 5
- 238000005538 encapsulation Methods 0.000 claims description 5
- 230000005669 field effect Effects 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 108091008695 photoreceptors Proteins 0.000 claims description 3
- 238000006557 surface reaction Methods 0.000 claims description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims 1
- 239000004973 liquid crystal related substance Substances 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 197
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 239000000178 monomer Substances 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 14
- 230000032258 transport Effects 0.000 description 14
- 239000010408 film Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 10
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 229920000547 conjugated polymer Polymers 0.000 description 7
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920000123 polythiophene Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003682 fluorination reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920006120 non-fluorinated polymer Polymers 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 125000005259 triarylamine group Chemical group 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 150000003577 thiophenes Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical class C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 description 2
- RICKKZXCGCSLIU-UHFFFAOYSA-N 2-[2-[carboxymethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]ethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]acetic acid Chemical compound CC1=NC=C(CO)C(CN(CCN(CC(O)=O)CC=2C(=C(C)N=CC=2CO)O)CC(O)=O)=C1O RICKKZXCGCSLIU-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- -1 aromatic radicals Chemical class 0.000 description 2
- 125000005018 aryl alkenyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 150000001716 carbazoles Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- XXPBFNVKTVJZKF-UHFFFAOYSA-N dihydrophenanthrene Chemical class C1=CC=C2CCC3=CC=CC=C3C2=C1 XXPBFNVKTVJZKF-UHFFFAOYSA-N 0.000 description 2
- 229920000775 emeraldine polymer Polymers 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 125000004404 heteroalkyl group Chemical group 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- PJULCNAVAGQLAT-UHFFFAOYSA-N indeno[2,1-a]fluorene Chemical class C1=CC=C2C=C3C4=CC5=CC=CC=C5C4=CC=C3C2=C1 PJULCNAVAGQLAT-UHFFFAOYSA-N 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000004866 oxadiazoles Chemical class 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical class C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003216 pyrazines Chemical class 0.000 description 2
- 150000004892 pyridazines Chemical class 0.000 description 2
- 150000003230 pyrimidines Chemical class 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical class C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 1
- 125000004958 1,4-naphthylene group Chemical group 0.000 description 1
- VBLXCTYLWZJBKA-UHFFFAOYSA-N 2-(trifluoromethyl)aniline Chemical compound NC1=CC=CC=C1C(F)(F)F VBLXCTYLWZJBKA-UHFFFAOYSA-N 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005015 aryl alkynyl group Chemical group 0.000 description 1
- 125000005264 aryl amine group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229940043397 deconex Drugs 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004827 dibenzo-1,4-dioxins Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002979 perylenes Chemical class 0.000 description 1
- 150000002987 phenanthrenes Chemical class 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 150000002988 phenazines Chemical class 0.000 description 1
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 150000005030 phenoxathiins Chemical class 0.000 description 1
- 125000001644 phenoxazinyl group Chemical class C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920000015 polydiacetylene Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 150000003252 quinoxalines Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Inorganic materials [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000005029 thianthrenes Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/115—Polyfluorene; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to an optoelectronic device comprising on a substrate a first layer and a second layer, characterized in that the first layer comprises an electrode material with fluorine-containing groups and the second layer comprises a polymer having fluorine-containing groups, wherein between a part of the fluorine-containing groups the first layer and the second layer consists of an adhesive fluorine-fluorine interaction.
- the invention further relates to the use of the optoelectronic device and to a method for producing the optoelectronic device according to the invention.
- OLED organic light-emitting diodes
- PLED Polymeric light emitting diodes
- the above arrangement represents the general structure of an optoelectronic device, wherein different layers can be combined, so that in the simplest case there is an arrangement of two electrodes, between which an organic layer is located.
- the organic semiconductor layer in this case fulfills all functions, including the emission of light.
- Such a system is described, for example, in WO 9013148 A1 on the basis of poly (p-phenylenes).
- Typical hole transport materials in SMOLEDs are, for example, di- and triarylamines, thiophenes, furans or carbazoles, which are also investigated and used in photoconductor applications.
- the compounds used in a SMOLED can often be cleaned by sublimations and are thus available in purities greater than 99 percent available.
- Polymers OLED materials are therefore usually applied by coating from solution.
- the preparation of a multilayered organic structure by solution coating requires that the solvent be incompatible with the respective preceding layer so as not to redissolve, swell, or even destroy it.
- the choice of solvent proves to be difficult, since the organic compounds used usually have similar properties, in particular similar dissolution properties.
- EP 0 637 899 A1 discloses an electroluminescent device comprising one or more organic layers, one or more of the layers being obtained by thermal or radiation-induced crosslinking.
- thermal crosslinking is that the polymeric layers are exposed to a relatively high temperature, which in part leads to the destruction of the corresponding layer or to the formation of undesired by-products.
- Crosslinking with actinic radiation often requires molecules or moieties which can initiate radical, cationic or anionic polymerization.
- such molecules or molecular moieties may have negative effects on the function of an optoelectronic device.
- the use of high-energy actinic radiation is problematic.
- the object of the present invention was therefore to provide an optoelectronic device which comprises a plurality of specialized functional layers which can be deposited from solution or dispersion, in each case adhere well to one another, ie ensure good contact, and can be replaced by a subsequent one
- the electrode is a highly conductive polymer or consists of an ITO or IZO layer and a conductive polymer.
- the second layer comprises a hole injection function and / or an emitter function.
- conductive polymers for hole injection and transport polymers made conductive by doping (oxidatively or by acids) are preferably used in all embodiments.
- PEDOT doped with polystyrene sulfonic acid (PSS) is available, for example, from H. C. Starck as Clevios P AI 4083 A, PSS doped PANI as PAT 020 from Merck KGaA. In the mentioned embodiment, however, all other known buffer materials can also be used.
- the optoelectronic device comprises an additional layer (or several additional layers).
- the additional layer also comprises compounds with fluorine-containing groups.
- the additional layer can be one Polymer having fluorinated groups, a partially fluorinated polymer or a polymer having fluorinated or perfluorinated side groups, an oligomer having fluorinated groups or a fluorinated molecule.
- the additional layer is preferably a charge injection layer, an emitter layer, a barrier layer and / or a combination of the cited.
- the polymer of the further layer has at least one emitter function.
- the polymer with emitter function should emit light of different wavelengths. This can be achieved by providing different emitters in one or more polymers or a blend in the layer.
- a preferred embodiment of the invention comprises, for example, a multilayer arrangement for a white light emitter, comprising an intermediate layer and a blue polymer layer, both of which adhere via FF interactions, and a yellow emitting layer, the contact of which can also be enhanced by fluorine-fluorine interactions.
- the yellow triplet emitter may be a true yellow emitter or an emitter composed of a red and green emitter.
- the device may comprise multiple layers of polymers with hole conductor function, wherein the hole conductors have energetically different highest occupied molecular orbitals (HOMO).
- HOMO highest occupied molecular orbitals
- the last applied polymer layer with hole conductor function has an energetically high lowest unoccupied molecular orbital (LUMO). In this way, the last-applied polymer layer is an electron-blocking layer.
- LUMO lowest unoccupied molecular orbital
- the device may comprise multiple layers of polymers having electron conductor function, the electron conductors having energetically different lowest unoccupied molecular orbitals (LUMO).
- LUMO lowest unoccupied molecular orbitals
- the polymer layer having an electron conductor function applied first has an energetically low highest occupied molecular orbital (HOMO).
- HOMO highest occupied molecular orbital
- a preferred embodiment thus comprises a multilayer arrangement comprising a plurality of (partially) fluorinated polymeric hole conductors and / or electron conductors having different HOMO and LUMO energies and corresponding electron or hole blocking function.
- improved hole or electron injection due to graded barrier steps can be achieved and the charge recombination can be efficiently trapped in the emission layer.
- the functions of charge transport and blocking are strengthened by the good adhesion of the fluorinated layers to each other and the resulting good contact.
- the optoelectronic device according to the invention further comprises a cathode and preferably an encapsulation.
- the object according to the invention is also achieved by a method for producing an optoelectronic device, comprising
- the first layer is an electrode which is provided with fluorine-containing groups before, during or after application to the substrate.
- the electrode used is indium tin oxide (ITO) or indium zinc oxide (IZO).
- the fluorine-containing groups are preferably applied to the electrode after application of the electrode to the substrate via a surface reaction or CF 4 plasma treatment.
- the electrode is a conductive polymer and the fluorine-containing groups are preferably introduced into the conductive polymer before the electrode is applied to the substrate. This can be done by chemical modification of the
- Polymers themselves fluorination reactions on the polymer), by the use of fluorinated monomers in the polymer synthesis or by the use of (partially) fluorinated dopants (such as polystyrene sulfonic acid, available as Liquion Solution LQ 1115, 110 EW) can be achieved.
- a plasma treatment carried out after the deposition of the layer is likewise possible.
- an electrode consisting of a combination of ITO or IZO with a conductive polymer, again strengthening the contact by a CF 4 plasma treatment of ITO or IZO and fluorine-containing groups in the conductive polymer.
- the second layer it is preferable to use a partially fluorinated polymer, a perfluorinated side group polymer, a fluorinated group-containing oligomer or a fluorinated molecule. It is further preferred that the second layer has a charge injection function, an emitter function, has a barrier function or combinations of said functions.
- the additional layer preferably comprises a charge injection function (hole or electron injection function), an emitter function, a barrier function or combinations of said functions.
- the device comprises a layer (or multiple layers) with small molecules or oligomers. This is preferably applied as the last layer (in front of a cathode).
- the coating may be applied by solution coating, by printing, by vapor deposition or by other methods known in the art.
- an adhesive fluorine-fluorine interaction exists between a part of the fluorine-containing groups of the first layer and the respective further layers.
- the application of a cathode and the application of an encapsulation to the optoelectronic device preferably take place.
- One part of the fluorine-containing groups means that about 10 to 100%, preferably 50 to 100% and particularly preferably 90 to 100% of the fluorine-containing groups interact, for example the distance between the fluorine atoms in order to interact with one another At least, the distance of the fluorine atoms from one another is such that an attractive FF interaction occurs, comparable to the interaction in hydrogen bonds With respect to the interaction of the layers with one another, the number of fluorine groups should be The portion of the interacting groups should be as high as possible, so that each fluorine-bearing group of the deposited layer in the second step a Pendant on the previously deposited (or plasma-modified) layer finds.
- a polymer in a layer according to the invention preferably comprises from 0.5 to 100%, particularly preferably from 1 to 50% and in particular from 1 to 25% of fluorine-containing groups, based on the repeat units of the polymer.
- 100% means that each
- Repeating unit of the polymer has fluorine-containing groups.
- the fluorine-containing groups R f preferably have the general formula C x HyF 2 , where x> 0, y ⁇ 0 and z> 1 and none, one or more CH 2 groups, which may also be adjacent, may be replaced by O, S, Se, Te, Si (R 1 ) 2 , Ge (R 1 ) 2 , NR 1 , PR 1 , CO, P (R 1 ) O, where R 1 is the same or different at each occurrence is a straight-chain, branched or cyclic alkyh alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, heteroaryl or heteroalkyl group, where one or more nonadjacent carbon atoms of the nonaromatic moieties are also represented by O, S, CO 1 COO or OCO can be replaced, with the proviso that two radicals R 1 can also form ring systems with one another.
- Preferred groups include, for example, F, CF 3 , C 2 F 5 , CF 3 (CH 2 ) a S, CF 3 CF 2 S or (CF 3 - (CH 2 ) a ) 2 N, where a is preferably an integer of 0 to 5 represents.
- Preferred materials for the substrate are e.g. As glasses and films that ensure adequate mechanical stability and barrier effect.
- the first layer is preferably on the substrate, and usually serves as an electrode. It is particularly preferred to apply indium tin oxide (ITO) or indium zinc oxide (IZO) to the substrate, which is usually done by sputtering. This is followed by fluorination, for example by a CF 4 plasma treatment.
- ITO indium tin oxide
- IZO indium zinc oxide
- a conductive polymer can be applied to the substrate, for example by coating from solution.
- the conductive polymer is preferably selected from PEDOT and PANI.
- the conductive polymer is a polymer which preferably carries fluorine-containing groups, for example fluorinated PEDOT or PANI.
- the polymer is preferably doped and can thus function as a charge injection layer.
- the polymer is a
- Polythiophene derivative more preferably poly (3,4-ethylenedioxy-2,5-thiophene) (PEDOT) or polyaniline (PANI).
- the polymers are preferably doped with polystyrene sulfonic acid or other polymer-bound Brönsted acids and thus brought into a conductive state.
- the conductive polymer preferably contains fluorine-containing groups R f (for example as defined above).
- PEDOT is commercially available, for example from HC Stark. It is usually doped with polystyrene sulfonic acid as PEDOTPSS. PEDOT is a conjugated polymer and can carry positive charges. Like PANI, it is a transparent polymer and is therefore excellently suited as a building block in an optoelectronic device.
- the incorporation of fluorine-containing groups in PEDOT is advantageously carried out in the preparation of the polymer, wherein fluorinated monomers can be used and copolymerized accordingly. It is also possible to use fluorinated or partially fluorinated polystyrenesulphonic acid (or its derivatives and copolymers). use. It is also possible, as with PANI, to fluorinate an applied polymer layer, for example by means of CF 4 plasma treatment.
- Polyaniline is a conjugated polymer consisting of oxidative and acid-catalyzed coupled aniline monomers.
- Polyaniline is doped directly after synthesis (Emeraldine Salz, ES).
- the dopant is the acid
- Non-doped PANI appears blue, doped PANI green and the reduced forms yellowish.
- aniline can be copolymerized together with aniline derivatives, for example by using aniline monomers having substituents with fluorine-containing radicals R f (for example as defined above), for example 2-trifluoromethylaniline or similar compounds , but here, too, the dopant (PSS) can carry the (partially) fluorinated groups.
- the first layer is an ITO or an IZO layer
- a conductive polymer is preferably present in the second layer. It is also possible that the second layer consists of the conductive polymer itself.
- the second layer comprises a hole injection function, and further, it is preferable that the second layer comprises a hole transport function. Both functions can be provided, for example, by doped polythiophene derivatives or polyanilines. Likewise preferred for the purposes of this invention, the second layer may comprise an emitter function. This can be done, for example, by copolymerizing emitter compounds or photoluminescent compounds with the monomers of the corresponding (conductive) polymer. The emitter compounds or photoluminescent
- Compounds may be located in the backbone or side chain of the conductive polymer or may be grafted at appropriate locations, for example. Likewise, it is possible to use monomeric or polymeric emitter compounds which preferably have fluorine-containing groups.
- the optoelectronic device preferably comprises an additional layer. It is likewise preferred that, in addition to the one additional layer, further additional layers are present in the device.
- the additional layer (or layers) comprise compounds having fluorine-containing groups, preferably as defined above.
- the at least one additional layer may also be a polymer having fluorine-containing groups, a partially fluorinated polymer or a polymer having fluorinated or perfluorinated side groups, an oligomer having fluorinated groups, or a fluorinated molecule (small molecule).
- the optoelectronic device is characterized in that an adhesive fluorine-fluorine interaction exists between a part of the fluorine-containing groups of the additional layer and the respective preceding layer.
- the additional layer may be a charge injection layer (hole or electron injection layer), a charge transport layer (hole or electron transport layer), an emitter layer, a hole or electron blocking layer and / or a combination thereof.
- the additional layer can combine several functions in one layer, or that several additional layers assume the corresponding functions.
- a classical structure consisting of substrate, electrode, multifunctional layer and cathode or a structure as in the case of a "small molecule OLED" is possible, namely a construction
- one or more of the layers may be combined with each other, or the construction of polymeric layers may be combined with layers as known from a SMOLED.
- components can be vapor-deposited or printed, if desired, or components can be applied from solution, the components preferably having fluorine-containing groups.
- the optoelectronic device is suitable as an organic or polymeric light-emitting diode, as an organic solar cell (O-SC, eg WO 98/48433, WO 94/05045), as an organic field effect transistor (O-FETs), as organic switching element (O-IC, eg WO 95/31833, WO 99/10939), as organic field quenching element (FDQ, eg US 2004/017148), as organic optical amplifier, as organic Photoreceptor, as an organic photodiode or as an organic laser diode (O-LASER, eg, WO 98/03566) and can be used accordingly.
- O-SC organic solar cell
- O-FETs organic field effect transistor
- O-IC organic switching element
- FDQ organic field quenching element
- FDQ organic field quenching element
- O-LASER organic laser diode
- oligo- or poly (triarylamines), oligo- or poly (thiophenes) and copolymers which contain a high proportion of these units.
- the device is structured accordingly (depending on the application), contacted and finally hermetically sealed because the life of such devices drastically shortened in the presence of water and / or air. It may also be preferred to use a conductive, doped polymer as the electrode material for one or both of the electrodes and not to introduce an intermediate layer of conductive, doped polymer.
- electrode and counter electrode For applications in O-FETs and O-TFTs, it is also required that the structure except electrode and counter electrode (source and drain) contain a further gate, which is characterized by an insulator layer with a generally high (or rarely low ) Dielectric constant is separated from the organic semiconductor. In addition, it may be useful to bring in the device even more layers.
- the electrodes are chosen such that their potential coincides as well as possible with the potential of the adjacent organic layer, in order to ensure the most efficient electron or hole injection possible.
- low work function metals, metal alloys or multilayer structures of various metals are preferable, such as alkaline earth metals, alkali metals, main group metals or lathanoids (eg, Ca, Ba, Mg, Al, In, Mg, Yb, Sm 1, etc.).
- alkaline earth metals alkali metals
- main group metals or lathanoids eg, Ca, Ba, Mg, Al, In, Mg, Yb, Sm 1, etc.
- Metals which have a relatively high work function, such as. B. Ag, which then usually combinations of metals, such as Ca / Ag or Ba / Ag are used. It may also be preferred to introduce between a metallic cathode and the organic semiconductor a thin intermediate layer of a material with a high dielectric constant. Suitable examples of this are, for example, alkali metal or alkaline earth metal fluorides, but also the corresponding oxides (for example LiF, Li 2 O, BaF 2 , MgO, NaF, etc.). The layer thickness of this layer is preferably between 1 and 10 nm. As an anode, high work function materials are preferred. Preferably, the anode has a potential greater than 4.5 eV. Vacuum up.
- metals with a high redox potential such as Ag, Pt or Au
- metal / metal oxide electrons for example Al / Ni / NiO x , Al / PtO x
- at least one of the electrodes must be transparent to allow either the irradiation of the organic material (O-SC) or the outcoupling of light (OLED / PLED, O-LASER).
- a preferred construction uses a transparent anode.
- Preferred anode materials here are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO), which have fluorine-containing groups.
- ITO indium tin oxide
- IZO indium zinc oxide
- the layer thickness is preferably between 10 and 500 nm, more preferably between 20 and 250 nm
- polythiophene in particular poly (3,4-ethylenedioxy-2,5-thiophene) (PEDOT) and polyaniline (PANI)
- PEDOT poly(3,4-ethylenedioxy-2,5-thiophene)
- PANI polyaniline
- conductive polymers are polythiophene (PTh), poly (3, 4-ethylenedioxythiophene) (PEDOT), polydiacetylene, polyacetylene (PAc), polypyrrole (PPy),
- Polyisothianaphthene PITN
- polyheteroarylenevinylene PArV
- the heteroarylene group is e.g. May be thiophene, furan or pyrrole
- PpP poly-p-phenylene
- PPS polyphenylene sulfide
- PPN polyperinaphthalene
- PPc polyphthalocyanine
- the doping is usually carried out by acids or by oxidizing agents.
- the doping is preferably carried out by polymer-bound Brönsted acids. Particularly preferred for this purpose are polymer-bound sulfonic acids, in particular poly (styrenesulfonic acid), poly (vinylsulfonic acid).
- the conductive polymer for the charge injection layer fluorine-containing groups, whereby after application from solution and removal of the solvent, a fixation of the layer by adhesive FF interactions occurs.
- the polymer preferably contains the emitter layer in addition to emitting
- Repeating units further repeating units, which also preferably have fluorine-containing groups or substituents. It may be a single polymeric compound or a blend of two or more polymeric compounds or a blend of one or more polymeric compounds with one or more low molecular weight organic compounds.
- the organic emitter layer can preferably be applied by coating from solution or by various printing methods, in particular by ink-jet printing methods.
- the polymeric compound and / or the further compounds preferably have fluorine-containing
- the layer thickness of the organic semiconductor is, depending on the application, preferably from 10 to 500 nm, particularly preferably from 20 to 250 and in particular from 30 to 120 nm.
- Preferred repeating units in the polymer of the emitter layer include, but are not limited to, for example, the compounds shown below:
- Rf is a fluorinated radical of the general formula C x H y F z , where x> 0, y> 0 and z> 1 and none, one or more CH 2 groups, which may also be adjacent, denoted by O , S, Se, Te, Si (R 1 ) 2 , Ge (R 1 ) 2) NR 1 , PR 1 , CO 1 P (R 1 ) O may be replaced, wherein R 1 and R are the same or different at each occurrence a straight-chain, branched one
- Arylalkinyl-, heteroaryl or heteroalkyl group wherein one or more non-adjacent C atoms of the non-aromatic moieties may be replaced by O, S, CO, COO or OCO, with the proviso that two radicals R 1 also form ring systems with each other can.
- Q Preferred groups include, for example F, CF 3, C 2 Fs, CF 3 (CH 2) a S, CF 3 CF 2 S or (CF 3 - (CH 2) a) 2 N, where a is preferably an integer of O to 5 represents.
- preferred polymers or fluorine-containing polymers are conjugated polymers or partially conjugated polymers which contain sp 2 -hybridized carbon atoms in the main chain which may also be replaced by corresponding heteroatoms.
- conjugate is also designated if, for example, arylamine units and / or certain heterocycles (ie conjugation via N, O or S atoms) and / or organometallic complexes (ie conjugation via the metal atom ) are located.
- Typical representatives of conjugated polymers are poly-5-para-phenylenevinylenes (PPV), polyfluorenes, polyspirobifluorenes, polyphenanthrenes, polydihydrophenanthrenes, polyindenofluorenes, Systems that are broadly based on poly-p-phenylenes (PPP), and derivatives of these structures, especially those derivatives having fluorine-containing groups.
- PPP poly-5-para-phenylenevinylenes
- PPP polyfluorenes
- polyspirobifluorenes polyphenanthrenes
- polydihydrophenanthrenes polydihydrophenanthrenes
- polyindenofluorenes Systems that are broadly based on poly-p-phenylenes (PPP), and derivatives of these structures, especially those derivatives having fluorine-containing groups.
- Group 1 structural units representing the polymer backbone.
- Group 2 structural units which increase the hole injection and / or transport properties of the polymers.
- Group 3 structural units which increase the electron injection and / or transport properties of the polymers.
- Group 4 Structural units comprising combinations of Group 2 and Group 3 individual units.
- Group 5 Structural units showing the morphology and / or the
- Group 6 structural units which change the emission characteristics to such an extent that electrophosphorescence can be obtained instead of electrofluorescence.
- Group 7 structural units that improve the transition from singlet to triplet state. Suitable and preferred units for the abovementioned groups are described below, these preferably having the fluorine-containing groups defined according to the invention.
- Preferred group 1 units are, in particular, those which contain aromatic or carbocyclic structures having 6 to 40 C atoms.
- Suitable and preferred moieties include fluorene derivatives, e.g. in EP 0842208, WO 99/54385, WO 00/22027, WO 00/22026 and WO 00/46321, indenofluorenes, furthermore spirobifluorene derivatives, e.g. in EP 0707020, EP 0894107 and WO 03/020790, phenanthrene derivatives or dihydrophenanthrene derivatives, e.g. disclosed in WO 2005/014689. It is also possible to use a combination of two or more of these monomer units, e.g.
- Preferred units for the polymer backbone are, in addition to the units of the formula (1), in particular spirobifluorene, indenofluorene, phenanthrene and dihydrophenanthrene derivatives.
- Particularly preferred units of group 1 are divalent units according to the following formulas, wherein the dotted lines represent the linkages to the adjacent units:
- R 2 is the same or different at each occurrence H, a straight-chain, branched or cyclic alkyl or alkoxy chain having 1 to 22 carbon atoms, in which also one or more non-adjacent C atoms by O, S, CO, O-CO , CO-O or O-CO-O may be replaced, wherein one or more H atoms may be replaced by fluorine, an aryl or aryloxy group having 5 to 40 carbon atoms, in which also one or more C atoms may be replaced by O, S or N, which may also be substituted by one or more non-aromatic radicals R 2 , or F, CN, N (R 3 ) 2 or B (R 3 ) 2 ; and R 3 is the same or different at each occurrence H, a straight-chain, branched or cyclic alkyl chain having 1 to 22 carbon atoms, in which one or more non-adjacent C atoms by O, S, CO, O-CO, CO- O or
- Group 2 - Structural units which increase the hole injection and / or transport properties of the polymers:
- R 11 has one of the meanings given above for R 2
- the various formulas at the free positions may also be additionally substituted by one or more substituents R 11 and the symbols and indices mean:
- n is the same or different at every occurrence O, 1 or 2
- p is identical or different at each occurrence 0, 1 or 2, preferably 0 or 1
- o is identical or different at each occurrence 1, 2 or 3, preferably 1 or 2,
- Ar 11 , Ar 13 are the same or different at each occurrence and are an aromatic or heteroaromatic ring system having 2 to 40 C atoms, which may be monosubstituted or polysubstituted by R 11 or may also be unsubstituted; the possible substituents R 11 can potentially be located at any free position,
- Ar 12 , Ar 14 are the same or different on each occurrence Ar 11 , Ar 13 or a substituted or unsubstituted stilbenylene or tolanylene unit,
- Ar 15 is identical or different at each occurrence either a system according to Ar 11 or an aromatic or heteroaromatic ring system having 9 to 40 aromatic atoms (C or heteroatoms), which may be monosubstituted or polysubstituted by R 11 or unsubstituted and which at least two condensed rings; the mmöglglichischen SSheubb ⁇ stituenten R 11 can potentially sit in any free position.
- Group 3 - Structural units which increase the electron injection and / or transport properties of the polymers:
- Particularly preferred group 3 units are divalent units according to the following formulas, wherein the dotted lines represent the linkages to the adjacent units:
- Group 4 - Structural units comprising combinations of Group 2 and Group 3 individual units:
- Preferred group 6 units are those of the following formulas wherein the dashed lines represent the linkages to the adjacent units:
- M is Rh or Ir
- Y has the meaning given above, and the various formulas may be substituted at the free positions by one or more substituents R »11 as defined above.
- carbazole and bridged carbazole dimer units are contemplated, e.g. in WO 04/070772 and WO 04/113468.
- ketones, phosphine oxides, sulfoxides and similar compounds such as e.g. in WO 2005/040302 A1.
- the polymer may also further contain metal complexes bound in the main or side chain, which are generally composed of one or more ligands and one or more metal centers.
- polymers which additionally contain one or more units selected from groups 1 to 7.
- the polymers contain units which improve the charge transport or the charge injection, ie units from group 2 and / or 3; particularly preferred is a proportion of 1 to 30 mol% of these units; very particular preference is given to a proportion of from 2 to 10 mol% of these units.
- Group 1 units from Group 2 and / or 3 and units from Group 5.
- the polymers can be linear, branched or crosslinked.
- the copolymers according to the invention may have random, alternating or block-like structures or alternatively have several of these structures in turn. How copolymers having block-like structures can be obtained and which further structural elements are particularly preferred for this purpose are described in detail, for example, in WO 2005/014688. This font is via quote part of the present application.
- the polymers are typically prepared by polymerization of one or more types of monomers. Suitable polymerization reactions are known in the art and described in the literature. Particularly suitable and preferred polymerization and coupling reactions which all lead to C-C linkages are those according to SUZUKI, YAMAMOTO, SILHOE, HECK, NEGISHI, SONOGASHIRA or HIYAMA.
- the C-C linkages are preferably selected from the groups of the SUZUKI coupling, the YAMAMOTO coupling and the STILLE coupling.
- polystyrene resin it may also be preferred not to use the polymer as a pure substance, but as a mixture (blend) together with further optional polymeric, oligomeric, dendritic or low molecular weight substances. These can for example improve the electronic properties or emit themselves. Such blends are therefore also part of the present invention.
- Polymer solutions or solutions of small molecules are produced can, is known in the art and, for example, in WO 02/072714, the
- solutions and formulations may optionally contain one or more additives.
- the invention also provides a process for producing an optoelectronic device, comprising the a) applying a first layer to a substrate, and b) applying a second layer, wherein the first layer is an electrode which, before, during or after application to the Substrate is provided with fluorine-containing groups.
- the electrode used is indium tin oxide (ITO) or indium zinc oxide (IZO).
- ITO indium tin oxide
- IZO indium zinc oxide
- Substrate applied to the electrode via a surface reaction or CF 4 plasma treatment As a result, different fluorine-containing groups are formed on the surface of the electrode, for example CF 3 or even individual fluorine atoms which combine with the ITO or IZO surface.
- the substrate used according to the invention is glass or a polymer film, preferably glass.
- the electrode is a highly conductive polymer or a two-layer electrode consisting of ITO / IZO and conductive polymer, and the fluorine-containing groups are introduced into the conductive polymer prior to application of the electrode to the substrate.
- the fluorination is carried out by methods of the prior art, for example by polymerizing fluorinated monomers or by fluorinating the finished polymer.
- Molecules are used. Likewise, the emitters defined above can be used in the method according to the invention.
- a film of a fluorinated polyaniline (PANI) was applied to the modified ITO layer by spin-coating from aqueous dispersion (PBM-001, Merck KGaA). After application of the film, this was baked at 180 0 C for 10 minutes.
- PANI fluorinated polyaniline
- a homogeneous film was obtained (layer thickness: 70 nm), which could not be washed off again by treatment with solvents, ie it adhered very well to it despite the fluorinated ITO surface. This is due to the interfacial fluorine-fluorine interaction, which surprisingly results in good adhesion, resulting in improved and more homogeneous charge injection from the anode to the polymer in an OLED constructed thereof.
- Example 2 The layer structure obtained in step b) was used further in Example 2.
- Step b) Applying a layer of a conductive non-fluorinated polymer
- FIG. 2 shows the structure according to the invention, in which the layer structure produced in Example 1 is coated with a further layer of a fluorinated polymer by spin-coating.
- Example 1 The layer structure obtained in Example 1 was spin-coated with another layer of a non-fluorinated polymer.
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Abstract
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US11/923,522 US8236902B2 (en) | 2006-10-24 | 2007-10-24 | Fluorocarbon mediated polymer blends and methods for making thereof |
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US20150155494A1 (en) * | 2012-07-13 | 2015-06-04 | Merck Patent Gmbh | Organic electronic device comprising an organic semiconductors formulation |
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KR101534941B1 (ko) * | 2013-11-15 | 2015-07-07 | 현대자동차주식회사 | 도전성 전극패턴의 형성방법 및 이를 포함하는 태양전지의 제조방법 |
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- 2008-10-24 EP EP08841820.7A patent/EP2203945B1/de active Active
- 2008-10-24 WO PCT/EP2008/009020 patent/WO2009053088A1/de active Application Filing
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US20110068329A1 (en) | 2011-03-24 |
KR101508800B1 (ko) | 2015-04-06 |
KR20100101569A (ko) | 2010-09-17 |
EP2203945B1 (de) | 2014-04-16 |
CN102037579B (zh) | 2015-07-08 |
WO2009053088A1 (de) | 2009-04-30 |
CN102037579A (zh) | 2011-04-27 |
JP2011501369A (ja) | 2011-01-06 |
US8637853B2 (en) | 2014-01-28 |
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